JP2003200433A - Method for manufacturing fine processing mold and organic coloring matter dispersed substrate sheet used therein - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for manufacturing a fine processing mold having a fine and sharp smooth pattern in the atmosphere by utilizing laser beam having a relatively short wavelength and weak in intensity without using a mask. <P>SOLUTION: A powdery organic coloring matter is kneaded with a transparent polymer and the resulting kneaded mixture is ground and subsequently dissolved in a solvent to prepare an organic coloring matter dispersed polymer, which is, in turn, applied to a substrate sheet. After the solvent is removed, the obtained thin film 3 is irradiated with laser beam to manufacture the processed fine processing mold. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a microfabrication type manufacturing method and an organic dye-dispersed substrate used for the method. More specifically, a laser beam having a relatively short wavelength and weak intensity can be used.
In addition, a microfabricated manufacturing method capable of producing micron-order parts such as an optical element, a microgear, and a DNA chip having a fine, clear and smooth pattern in the atmosphere without using a mask, and a relatively thick And an organic dye-dispersed substrate having

[0002]

2. Description of the Related Art Photolithography is a method for forming a fine pattern on the surface of a substrate. In this method, a photoresist is applied to the surface of a substrate, and the photoresist is irradiated with ultraviolet rays or the like through a mask of a predetermined pattern prepared in advance, whereby a mask image is printed on the photoresist and the photoresist is used as a solvent. And the substrate is etched according to the pattern. Further, a technique has been proposed in which a fine processing mold is manufactured by using a laser drawing method, an electron beam, or a scanning probe microscope, and the fine processing is transferred by being pressed against a polymer layer formed on a substrate. However, in the photolithography method, it is necessary to separately manufacture a mask, while in the laser drawing method, an ultraviolet laser having an output of several MW is required, which causes a problem that the apparatus becomes large in size.

Here, there is a method of irradiating a thin film with a narrowed laser beam according to an arbitrary pattern as a technique for performing microfabrication on the thin film on the order of micrometers without requiring a large and expensive device. The metal fine particle-dispersed polymer film in which the metal fine particles are dispersed in the polymer film has a light absorption characteristic peculiar to the metal fine particles. It is possible to produce an arbitrary fine structure composed of concave portions formed in the irradiated portion. The present applicant discloses an optical recording medium (see, for example, Patent Document 1), a fine processing type (see, for example, Patent Document 2), a grating (see, for example, Patent Document 3) and the like using a metal fine particle dispersed polymer film. .

Further, since three-dimensional fine processing is required to perform complicated shape processing, a material capable of controlling the processing shape in the depth direction and a processing method therefor are required. For this reason, a thick film resist made of PMMA, epoxy, or urethane which is hardened or deteriorated by irradiation of X-rays or ultraviolet rays, which enables fine processing with a high aspect ratio, and a processing method thereof have been proposed. All resists are processed by exposure and development using a photomask, but the degree of freedom of the processed shape in the depth direction is low. For example, the processed shape in the depth direction has a vertical wall surface, and it is difficult to taper or obtain a processed shape with a sharp tip. In order to solve such problems, an exposure method using a moving mask and a processing method by lift-off have been proposed. However, there is a problem that the processing cost becomes very high because the process and the equipment become complicated.

In view of such problems, the present applicant has considered
A method and a fine pattern for manufacturing a fine patterning type that does not require a strong laser beam and can be processed by a laser beam having a relatively weak intensity in the visible range and has a fine and clear pattern in the atmosphere without using a mask. A method for producing a molded article having the above is provided in Japanese Patent Application No. 2001-231360.

That is, in the microfabrication type manufacturing method, a metal fine particle dispersion comprising a metal fine particle dispersion liquid in which metal fine particles are independently dispersed in a solvent or a protective polymer, a polymer matrix, and a solvent is spread on a substrate. To form a metal fine particle dispersed film, a step of producing a patterned master mold by irradiating a cured metal fine particle dispersed film with a laser beam, and forming and hardening a thin film of liquid silicone rubber on the master mold After that, the method is a method for producing a microfabricated mold, which comprises a step of removing the mold to produce a transfer mold of silicone rubber, and specifically illustrates ethyl cellulose, silicone, or the like as the polymer matrix. It is characterized in that it can be processed by a weak laser beam without requiring a strong laser beam such as an excimer laser or a YAG laser as in the conventional case.

[0007]

[Patent Document 1] Japanese Patent Laid-Open No. 2001-216680

[Patent Document 2] Japanese Patent Laid-Open No. 2001-310331

[Patent Document 3] Japanese Unexamined Patent Application Publication No. 2001-311810

[0008]

[Problems to be Solved by the Invention]

However, there is room for improvement in the above technique, and when ethyl cellulose or silicone is used as the polymer matrix, the periphery of the laser-machined hole entrance is raised, and a smooth pattern cannot be obtained. There was a problem. The above-mentioned drawbacks can be applied in a field in which the surface bulge such as a mask material at the time of processing is not a problem, but, for example, for a microcapillary electrophoresis chip that is attracting attention in the field of biochemistry, it is necessary to form a fine channel. It was difficult to apply.

Further, conventionally, since precious metal fine particles such as gold and silver are used, the cost of the treatment liquid is high and the wavelength of the laser light used is large, so that it is difficult to process a fine line. .

The present invention solves the above-mentioned problems, and it is possible to use a laser beam having a relatively short wavelength and a weak intensity, and moreover, it is fine and clear in the atmosphere without using a mask. Moreover, it is an object of the present invention to provide a method for manufacturing a microfabricated mold having a smooth pattern and an organic dye-dispersed substrate used for the method.

[0012]

In order to solve the above problems, according to the invention of claim 1, in a method for producing a mold having a fine pattern, a powdery organic dye is kneaded with a transparent polymer. After crushing, an organic dye-dispersed polymer was prepared by dissolving in a solvent, the organic dye-dispersed polymer was applied onto a substrate to remove the solvent, and the resulting thin film was irradiated with laser light to form a master mold. It is a method for producing a microfabrication mold, which is produced and molds a transfer mold from the master mold.

According to the second aspect of the present invention, in the method for producing a mold having a fine pattern, a powdery organic dye dispersion polymer obtained by kneading and pulverizing a powdery organic dye with a transparent polymer and a solvent. In a mold, heat and pressurize the resulting organic dye-dispersed substrate to irradiate a laser beam to prepare a master mold, and form a transfer mold from the master mold.

According to the third aspect of the present invention, at least the organic dye is selected from condensed azo type, isoindolinone type, quinacridone type, dikenopyrrolopyrrole type, anthraquinone type, dioxazine type, phthalocyanine type and perylene type. It is a method of manufacturing a microfabricated mold.

The invention according to claim 4 of the present application is the method for producing a microfabricated mold, wherein the transparent polymer is ethyl cellulose.

According to a fifth aspect of the present invention, there is provided an organic dye dispersion substrate in which an organic dye is dispersed in a transparent polymer, which is obtained by kneading and pulverizing a powdery organic dye with a transparent polymer and a solvent. Fill the mold with the organic dye-dispersed polymer, heat,
It is on the organic dye-dispersed substrate obtained by pressing.

[0017]

BEST MODE FOR CARRYING OUT THE INVENTION The organic dye used in the present invention forms pits having a diameter of several hundred nm by irradiation with a laser having a relatively short wavelength, and enables shallow hole processing and fine line processing. . Also, by dispersing an organic dye in a polymer, a film having a thickness of several hundreds of μm can be formed, and at the same time, the aspect ratio displayed by the depth ratio of the processed width (depth / width). Fine processing with a large ratio becomes possible. Organic dyes are cheaper than fine gold particles and, for example, 3, 4,
The 9,10-perylenetetracarboxylic acid diimide can absorb the same red light as the gold fine particles. When this sample is irradiated with laser light having a wavelength of 532 nm, grooves, holes, etc. of the order of μm become possible.

Examples of the above-mentioned organic dye include condensed azo dyes, isoindolinone dyes, quinacridone dyes, dikenopyrrolopyrrole dyes, anthraquinone dyes, dioxazine dyes,
It is at least one selected from phthalocyanine series and perylene series.

Specific examples of the above organic dyes include quinacridone, dianthraquinonyl red, benzimidazolone isoindolinone, polyazo, disazo, azomethine nickel, naphthol arsenic, thioindicophthalocyanine, phthalocyanine, perylene, perylene tetracarboxylic acid diimide. There is a molecular crystal such as. Alternatively, phthalocyanine, octacyanophthalocyanine, tetra-t-butylphthalocyanine, magnesium phthalocyanine, vanadyl phthalocyanine, copper phthalocyanine, zinc phthalocyanine, aluminum phthalocyanine, silicon phthalocyanine, copper tetra-t-butyl phthalocyanine, copper octacyanophthalocyanine, naphthalocyanine, copper naphthalocyanine. , Zinc naphthalocyanine, cobalt naphthalocyanine, vanadyl naphthalocyanine, octacyanonaphthalocyanine, tetracyanonaphthalocyanine, tetramethylnaphthalocyanine, tetraethylnaphthalocyanine, tetramethoxynaphthalocyanine, and the like.

The organic dye is pulverized, and the amount of the organic dye added in the organic dye-dispersed polymer is 2.8 to 6.7% by mass. If it is less than 2.8% by mass, the light energy of the laser beam cannot be fully utilized in the step of irradiating the laser beam, and it becomes difficult to form a fine and clear pattern, and the addition amount of the organic dye is 6. When it exceeds 7% by mass, the concentration is too high, the organic dye is decomposed, and a good dispersion liquid or dispersion film can be obtained.

As the transparent polymer, cellulose resins such as ethyl cellulose and nitrocellulose, acrylic resins such as polymethyl methacrylate and polyethyl methacrylate are used, and among them, ethyl cellulose has a good dispersibility of organic dyes. Is preferred.

Any solvent may be used as long as it can dissolve a transparent polymer, for example, α-terpineol, methanol, ethanol, toluene, p-xylene, water, carbitol, methacresol, N-methyl-2-pitaridone, dimethylformamide, It is preferable to use dimethylacetamide or the like.

The above-mentioned powdery organic dye and transparent polymer are kneaded in a mortar and crushed by a crusher to obtain an organic dye-dispersed polymer dissolved in a solvent. Further, a powdery organic dye is kneaded with a transparent polymer and a solvent and pulverized to obtain a powdery organic dye dispersion polymer.

Next, the manufacturing method of the microfabrication mold manufacturing method will be described below with reference to FIGS. As shown in FIG. 1, the above-mentioned powdery organic dye and transparent polymer are kneaded in a mortar on a surface 2 of a substrate 1 made of a resin made of glass, polymethylmethacrylate, polycarbonate, ABS resin, etc. After crushing, an organic dye dispersion polymer dissolved in a solvent is applied to form a thin film 3 having a thickness of 1 μm or more and dried. The thin film 3 can be formed on the surface of the substrate 1 by various methods such as spin coating, dipping, brush coating, and spraying. However, it is preferable to apply the coating as uniformly as possible, and spin coating is suitable. is there.

Subsequently, the substrate 1 on which the thin film 3 of the organic dye-dispersed polymer is formed is heated at room temperature or to remove the solvent, and then the thin film 3 is irradiated with laser light to form a pattern. Specifically, as shown in FIG. 2, the laser light 19 of the green laser as the light source 11 is adjusted to a predetermined intensity, and while entering the half mirror 14 in the optical microscope 13 while changing the optical path by several mirrors 12, The thin film 3 was narrowed down by the objective lens 15, and the thin film 3 placed on the XYZ stage 16 was irradiated for a predetermined time. While observing with the CCD camera 17 and the TV monitor 18 connected thereto, various patterns having concave and convex portions on the thin film 3 are formed while moving the XYZ stage 16 to manufacture the master mold 20.

Liquid silicone rubber was dropped on the master mold 20 to form a film having a thickness of 2 to 5 mm, and the film was polymerized at room temperature and then peeled off as shown in FIG. A microfabrication mold 22 which is 21 was manufactured.

The liquid silicone rubber used here is a liquid diorganopolysiloxane such as dimethylpolysiloxane and can be cured at room temperature or with slight heating. A linear, low-viscosity dimethylsiloxane having silanol groups at both ends and a deacetic acid type, dealcohol type, deoxime type, deamino type, deacetone type, deaminoxy type, dehydrogenation type, etc. A silicone rubber is obtained by containing a functional silane and adding a catalyst such as a metal carboxylate to this polymer.

Further, according to the present invention, it is necessary to repeatedly stack several tens of times or more in order to obtain a thick film of several hundreds of μm or more by a spin coating method or the like, and in order to solve this, the following method is also included. That is, as shown in FIG. 6, after a powdery organic dye dispersion polymer 30 obtained by kneading and pulverizing a powdery organic dye with a transparent polymer and a solvent is filled in a lower mold 31,
Compression molding is performed by heating and pressurizing at 140 to 150 ° C. by the upper mold 32. The obtained organic dye-dispersed substrate is a plate-like body having a thickness of 0.3 to 1 mm in which an organic dye is dispersed in a transparent polymer. If the heating temperature for compression molding exceeds 150 ° C., laser processing becomes difficult because the organic dye is aged and decomposed. On the other hand, when the temperature is lower than 140 ° C., the transparent polymer becomes difficult to melt, and a fine processing mold cannot be obtained.

Then, as in the above, the organic dye-dispersed substrate 3
3 is irradiated with laser light and processed to produce a master mold,
A transfer mold is molded from the master mold.

[0030]

EXAMPLES Next, specific methods of the present invention will be described below.

Examples 1 to 3 (Preparation of Organic Dye Dispersion Polymer) Powdery 3, 4, 9,
10-Perylene tetracarboxylic acid diimide 0.05-
A small amount of p-xylene was added to 0.02 g and 0.7 g of ethyl cellulose and kneaded in a mortar. After kneading, it was dried at room temperature for 24 hours, and powdery perylene-dispersed ethyl cellulose was obtained with a freeze pulverizer.

(Preparation of Dye Dispersion) 0.5 g of p-xylene was added to 0.5 g of crushed perylene-dispersed ethyl cellulose, and the mixture was stirred at room temperature for 24 hours.

(Film Forming Step) The above dye dispersion liquid was placed on a PMMA substrate by a spin coater (rotation speed: 5,000 rpm, 1 rpm).
After forming a film for 5 seconds), it was dried at 80 ° C. for 5 minutes.

(Laser processing) The objective lens (× 1
0, NA 0.25) focused laser light (wavelength 532n
m, output 28 mW) was scanned to form a pattern to prepare a master mold.

(Evaluation) The surface and cross-sectional shape of the master mold made of the perylene-dispersed ethyl cellulose film processed using a scanning electron microscope were observed. As a result, Example 1
In Nos. 3 to 3, no dye aggregation was visually observed. Also,
FIG. 4 shows a photograph of the microfabrication mold obtained by transferring the master mold obtained in Example 1 with dimethylpolysiloxane by an atomic force microscope, and FIG. 5 shows the same fine microstructure obtained in Example 3. The photograph which image | photographed the process type with the atomic force microscope is shown.

Comparative Example 1 A dispersion of 0.01 g of powdered 3,4,9,10-perylenetetracarboxylic acid diimide and 0.7 g of ethyl cellulose was prepared in the same manner as in Example 1 to form a film, which was then laser processed. However, it was not possible to form an arbitrary pattern.

Comparative Example 2 Ethyl cellulose was dissolved in p-xylene to form a film, which was then laser processed, but no arbitrary pattern was formed.

Comparative Example 3 Ethyl cellulose was dissolved in p-xylene, powdery 3,4,9,10-perylenetetracarboxylic acid diimide was added and stirred for 24 hours, but the dye did not disperse but precipitated.

Table 1 shows Examples 1 to 3 and Comparative Examples 1 to 3 above.

[0040]

[Table 1]

As described above, in the examples, the dispersion was in a good condition, and the dye was not aggregated even on the surface of the microfabricated mold, and the pattern formation was good.

Examples 4 to 10 and Comparative Example 4 (Preparation of Organic Dye Dispersion Polymer) As shown in Table 2, 3 g of ethyl cellulose was mixed with a predetermined amount of an organic dye (Microlith 2C-A: manufactured by Ciba Specialty Chemicals Co., Ltd.). ) And p-xylene were added in a small amount, the mixture was kneaded in a mortar, dried at room temperature, and pulverized with a freeze pulverizer to obtain powdery organic dye-dispersed ethyl cellulose.

[0043]

[Table 2]

(Preparation of Organic Dye Dispersion Substrate) 100
After keeping the temperature at 0 ° C., the lower mold is filled with powdery organic dye-dispersed ethyl cellulose, and the upper mold is pressed to a predetermined pressure. After pressurizing, the temperature was raised to 140 to 150 ° C. to melt, and then cooled to 100 ° C., and an organic dye-dispersed substrate having a thickness of 0.5 mm was taken out.

(Laser processing) A green laser beam (wavelength 532 nm, output 28 mW) focused by an objective lens (× 10, NA 0.25) is scanned on an organic dye dispersion substrate,
A master pattern was prepared by performing a line pattern and punching. The laser intensity on the irradiated surface was 23 mW, and the line pattern writing speed was 0.5 mm / sec.

(Evaluation) Scanning electron microscope observation of the above master type was performed. A photograph of Example 5, which is an example thereof, is shown in FIG.
Shown in. The processing shape changes depending on the dye concentration, and the processing depth becomes maximum and the processing width becomes minimum when the concentration is 3%. The results are shown in Table 3.

[0047]

[Table 3]

[0048]

As described above, in the invention described in the claims of the present application, a powdery organic dye is kneaded with a transparent polymer, pulverized, and then dissolved in a solvent to prepare an organic dye dispersion polymer. After the polymer is applied on the substrate to remove the solvent, the thin film obtained is irradiated with laser light to prepare a master mold, and the master mold is used in a method for producing a microfabrication mold to be a transfer mold. By irradiating a laser with a relatively short wavelength, a pit with a diameter of several hundred nanometers can be formed by irradiating a laser with a relatively short wavelength, making it possible to perform shallow hole processing and fine line processing. A film thickness of 100 μm can be produced, and at the same time, inexpensive fine processing with a large aspect ratio displayed by the ratio of the processing width and depth can be obtained. Further, in the method in which the organic dye-dispersed substrate is irradiated with the laser beam to be processed, the organic dye-dispersed substrate having a relatively large thickness can be obtained by fine processing with a large aspect ratio and at a low cost.

[Brief description of drawings]

FIG. 1 shows a method for manufacturing a microfabrication die according to the present invention,
It is a figure which shows the state which formed the thin film of the organic dye dispersion polymer on the board | substrate.

FIG. 2 shows a method for manufacturing a microfabrication die according to the present invention,
FIG. 3 is a diagram in which a thin film of an organic dye-dispersed polymer cured on a substrate is irradiated with laser light to produce a microfabricated mold.

FIG. 3 shows a method for manufacturing a microfabrication die according to the present invention,
It is a figure which has produced the transfer type on the master type.

FIG. 4 shows a photograph of the microfabricated mold obtained in Example 1 taken by an atomic force microscope.

FIG. 5 shows a photograph of the microfabricated mold obtained in Example 3 taken with an atomic force microscope.

FIG. 6 is a diagram showing a method in which a mold is filled with a powdery organic dye-dispersed polymer,
It is sectional drawing of the state which is producing the organic dye dispersion substrate obtained by heating and pressurizing.

FIG. 7 is an observation view of a master type scanning electron microscope in Example 5.

[Explanation of symbols]

1 substrate 3 thin film 5 ultraviolet rays 11 light source 13 Optical microscope 14 Half mirror 15 Objective lens 16 XYZ stage 19 laser light 20 master type 21 Transfer type 22 Micro processing type

Claims (5)

[Claims] 1. In a method for producing a mold having a fine pattern, a powdery organic dye is kneaded with a transparent polymer, pulverized, and then dissolved in a solvent to prepare an organic dye dispersion polymer. Is applied to the substrate to remove the solvent, the thin film obtained is irradiated with a laser beam to prepare a master mold, and a transfer mold is molded from the master mold. Method. 2. In a method for producing a mold having a fine pattern, a powdery organic dye-dispersing polymer obtained by kneading and pulverizing a powdery organic dye with a transparent polymer and a solvent is filled in a mold, A method for producing a microfabrication mold, comprising irradiating an organic dye-dispersed substrate obtained by heating and pressurizing with a laser beam to prepare a master mold, and molding a transfer mold from the master mold. 3. The organic dye is at least one selected from condensed azo dyes, isoindolinone dyes, quinacridone dyes, dikenopyrrolopyrrole dyes, anthraquinone dyes, dioxazine dyes, phthalocyanine dyes, and perylene dyes. 2. The method for manufacturing a microfabricated mold according to 2. 4. The method for producing a microfabricated mold according to claim 1, wherein the transparent polymer is ethyl cellulose. 5. An organic dye dispersion substrate in which an organic dye is dispersed in a transparent polymer, wherein the powdery organic dye is kneaded with a transparent polymer in a solvent and pulverized to obtain an organic dye dispersion polymer. An organic dye-dispersed substrate, which is obtained by filling a mold with, and heating and pressing.